Which phonons contribute most to negative thermal expansion in ScF3?
Source abstract
Abstract
Using calculations of the phonon distribution in ScF3 across the whole of reciprocal space, we show that the important phonons for the negative thermal expansion in this material are those associated with the rigid unit modes (RUMs) and associated quasi-RUMs. We discuss the role of the bond-bending flexibility within the ScF6 octahedra, and how this enables other phonons to make an additional but ultimately much weaker contribution to negative thermal expansion. These results inform recent discussions on the role of correlated atomic motions in giving rise to negative thermal expansion in ScF3.
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Research context
OpenAlex topics: Thermal Expansion and Ionic Conductivity · Thermodynamic and Structural Properties of Metals and Alloys · Advanced Battery Materials and Technologies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
College of Computer Science, Sichuan University 1 , Chengdu 610065, China
School of Mechanical Engineering, Dongguan University of Technology 2 , Songshan Lake, Dongguan, Guangdong 523000, China
School of Physical and Chemical Sciences, Queen Mary University of London 3 , Mile End Road, London E1 4NS, United Kingdom
ISIS Facility, Rutherford Appleton Laboratory, Harwell Campus 4 , Didcot, Oxfordshire OX11 0QX, United Kingdom
Funding
Engineering and Physical Sciences Research Council · National Natural Science Foundation of China
References (70)
Show source-provided references
1. Compounds that contract on heating10.1021/ic980253h ↗
2. Negative thermal expansion materials10.1039/a904297k ↗
3. Negative thermal expansion10.1088/0953-8984/17/4/r03 ↗
4. Negative thermal expansion: A review10.1007/s10853-009-3692-4 ↗
5. Two decades of negative thermal expansion research: Where do we stand?10.3390/ma5061125 ↗
6. Negative thermal expansion (thermomiotic) materials10.1016/B978-0-08-097774-4.00425-3 ↗
7. Negative thermal expansion in functional materials: Controllable thermal expansion by chemical modifications10.1039/c4cs00461b ↗
8. Negative thermal expansion and associated anomalous physical properties: Review of the lattice dynamics theoretical foundation10.1088/0034-4885/79/6/066503 ↗
9. Phonons and anomalous thermal expansion behaviour in crystalline solids10.1016/j.pmatsci.2017.10.002 ↗
10. Negative thermal expansion in framework structure materials10.1016/j.ccr.2021.214204 ↗
11. Pronounced negative thermal expansion from a simple structure: Cubic ScF310.1021/ja106711v ↗
12. Quantitative understanding of negative thermal expansion in scandium trifluoride from neutron total scattering measurements10.1103/physrevb.102.094105 ↗
13. Entropic elasticity and negative thermal expansion in a simple cubic crystal10.1126/sciadv.aay2748 ↗
14. New insights into the negative thermal expansion: Direct experimental evidence for the “guitar-string” effect in cubic ScF310.1021/jacs.6b02370 ↗
15. Localized symmetry breaking for tuning thermal expansion in ScF3 nanoscale frameworks10.1021/jacs.8b00885 ↗
16. Anharmonicity and scissoring modes in the negative thermal expansion materials ScF3 and CaZrF610.1103/physrevb.101.064306 ↗
17. Visualization and analysis of crystal structures using CrystalMaker software10.1515/zkri-2015-1869 ↗
18. On the application of mean-field and Landau theory to displacive phase transitions10.1080/00150199208016064 ↗
19. The determination of rigid-unit modes as potential soft modes for displacive phase transitions in framework crystal structures10.1107/s0108767393002545 ↗
20. Rigid unit modes in framework silicates10.1180/minmag.1995.059.397.07 ↗
21. Rigid-unit phonon modes and structural phase transitions in framework silicates10.2138/am-1996-9-1003 ↗
22. Distortions of framework structures10.1080/01411599608242398 ↗
23. Flexibility of network materials and the rigid unit mode model: A personal perspective10.1098/rsta.2018.0222 ↗
24. The rigid unit mode model: Review of ideas and applications10.1088/1361-6633/acc7b7 ↗
25. Geometrical origin and theory of negative thermal expansion in framework structures10.1111/j.1151-2916.1999.tb02001.x ↗
26. Structural relationship between negative thermal expansion and quartic anharmonicity of cubic ScF310.1103/physrevlett.107.195504 ↗
27. First-Principles study of Sc1−xTixF3 (x ≤ 0.375): Negative thermal expansion, phase transition, and compressibility10.1111/jace.13676 ↗
28. Negative thermal expansion in isostructural cubic ReO3 and ScF3: A comparative study10.1016/j.commatsci.2015.05.019 ↗
29. First-principles study of phonon anharmonicity and negative thermal expansion in ScF310.1103/physrevmaterials.3.033601 ↗
30. Interpretation of unexpected behavior of infrared absorption spectra of ScF3 beyond the quasiharmonic approximation10.1103/physrevb.93.214101 ↗
31. Large isotropic negative thermal expansion above a structural quantum phase transition10.1103/physrevb.92.134101 ↗
32. Negative thermal expansion near two structural quantum phase transitions10.1103/physrevmaterials.1.070603 ↗
33. Negative thermal expansion near the precipice of structural stability in open perovskites10.3389/fchem.2018.00545 ↗
34. Two-dimensional nanoscale correlations in the strong negative thermal expansion material ScF310.1103/physrevb.94.214102 ↗
35. Lattice dynamics and hydrostatic-pressure-induced phase transitions in ScF310.1134/1.1484991 ↗
36. The heat capacities of thermomiotic ScF3 and ScF3–YF3 solid solutions10.1007/s10853-015-8899-y ↗
37. Anomalous thermal conductivity and suppression of negative thermal expansion in ScF310.1103/physrevb.94.020303 ↗
38. Negative thermal expansion of ScF3: Insights from density-functional molecular dynamics in the isothermal-isobaric ensemble10.1103/physrevb.92.224302 ↗
39. Size effects on negative thermal expansion in cubic ScF310.1063/1.4959083 ↗
40. Negative thermal expansion of ScF3: First principles vs empirical molecular dynamics10.1088/1757-899x/503/1/012001 ↗
41. The thermal expansion of alkali halides at low temperatures10.1098/rspa.1965.0139 ↗
42. The thermal expansion of alkali halides at low temperatures - II. Sodium, rubidium and caesium halides10.1098/rspa.1973.0060 ↗
43. Theorie des festen zustandes einatomiger elemente10.1002/andp.19123441202 ↗
44. Zustand des festen Körpers10.1007/978-3-642-99531-6 ↗
45. The state of a solid body
46. Common origin of negative thermal expansion and other exotic properties in ceramic and hybrid materials10.1103/physrevb.89.214103 ↗
47. J. P. Rumsey , “The secret behind crystals that shrink when heated,” https://www.ornl.gov/news/secret-behind-crystals-shrink-when-heated; accessed: 19 September 2021 (2019).
48. On the calculation of the equilibrium and stiffness of frames10.1080/14786446408643668 ↗
49. Generalized gradient approximation made simple10.1103/physrevlett.77.3865 ↗
50. First principles methods using CASTEP10.1524/zkri.220.5.567.65075 ↗
51. Special points for Brillouin-zone integrations10.1103/physrevb.13.5188 ↗
52. Phonons and related crystal properties from density-functional perturbation theory10.1103/revmodphys.73.515 ↗
53. Variational density-functional perturbation theory for dielectrics and lattice dynamics10.1103/physrevb.73.155114 ↗
54. 1993
55. Simulation study of negative thermal expansion in yttrium tungstate Y2W3O1210.1088/0953-8984/27/18/185401 ↗
56. Acoustic phonons and negative thermal expansion in MOF-510.1039/c4cp01701c ↗
57. Framework flexibility and the negative thermal expansion mechanism of copper(I) oxide, Cu2O10.1103/physrevb.89.214115 ↗
58. The materials Project: A materials genome approach to accelerating materials innovation10.1063/1.4812323 ↗
59. See https://materialsproject.org for Materials project; accessed 26 September 2021 (2021).
60. See https://materialsproject.org/materials/mp-10694/ for ScF3, mp-10694; accessed 26 September 2021.
61. 2020
62. Colossal pressure-induced softening in scandium fluoride10.1103/physrevlett.124.255502 ↗
63. Negative thermal expansion and compressibility of Sc1−xYxF3 (x ≤ 0.25)10.1063/1.4836855 ↗
64. Solid solubility, phase transitions, thermal expansion, and compressibility in Sc1−xAlxF310.1016/j.jssc.2014.11.007 ↗
65. Spanier · 1926
66. Review: Pair distribution functions from neutron total scattering for the study of local structure in disordered materials10.1016/j.nucana.2022.100037 ↗
67. Pair distribution functions calculated from interatomic potential models using the General Utility Lattice Program10.1107/s0021889807016032 ↗
68. GULP: A computer program for the symmetry-adapted simulation of solids10.1039/a606455h ↗
69. The general utility lattice program (GULP)10.1080/0892702031000104887 ↗
70. The continuous melting transition of a three-dimensional crystal at a planar elastic instability10.1088/0022-3719/21/28/001 ↗